Phosphated blown oils



Patented Oct. 9, 1945 2.386.250 rirosrnh'rnn BLOWN ous James G. McNally and Joseph B. Dickey, Rochester, -N. Y., assignors to pany, Rochester, N. Y.,

Jersey No Drawing. Application Serial No.

Eastman Kodak Coma corporation of New July 15, 1943, 494,846

Claims. (Cl. 260-403) This invention relates to the preparation of.

a new type of phosphated and phosphited oils and more particularly to the preparation of phosphated blown naturally-occurring oils, fats and waxes. The present application is in part a continuation of our copending application, Ser. No. 285,208, filed July 18, 1939, now Patent No. 2,345,734.

It is well known that various oils may be caused to react with phosphoric or phosphorous acids to produce the corresponding phosphated or phosphited oils. The preparation of phosphoric acid esters of naturally occurring oils, such as castor oil, has been described, for example, in the U. S. patent to Chittick 2,142,998. In'this case, as in all other instances of which we are aware, the oil reacted with the phosphoric or phosphorous acid or other phosphating or phosphiting agent is, either a naturally occurring hydroxylated oil or an oil which has been hydroxylated by artificial means. In Patent 2,142,998, for example, a naturally occurring hydroxylated oil, such as castor oil, is phosphated by means of a. phosphating agent such as phosphorus oxychloride.

It has been shown that it is impossible to obtain a phosphated 0r phosphited oil by treating an oil such asneats-foot, olive, teaseed, or sperm oils and the like with phosphating or phosphiting agents such as phosphoric acid, phosphorous acid, phosphoi us oxychloride, phosphorus pentachloride, phosphorus trichloride and the like, since these oils are not hydroxylated oils, that is, they contain no free hydroxyl groups with which the phosphating or phosphiting agent can react.

This invention has phated and phosphited oils from naturally occurring oils. A further object is to produce phosphated oils from both naturally occurring hydroxylated oils and from oils, fats and waxes in which no free hydroxyl groups are normally present. A still further object is to provide a variety of phosphated and phosphited oils useful as surface-active agents, dispersing agents, textile conditioners, anti-static agents and for other purposes. Another object of our invention is to provide a process for the phosphation and phosphition of naturally occurring oils, fats and waxes which do not normally contain free hydroxyl groups. Still another object of our invention is to provide a process for producing phosphated and phosphited oils involving a mechanism of reaction not heretofore known or used for'the phosphation or phosphition of oils. Other objects will appear hereinafter.

These objects are accomplished by the followas an object to produce phosing invention which, in its broader aspects, involves, first blowing a naturally occurring, semidrying oil, fat or wax and thereafter treating the blown oil with aqueous solutions of phosphating or phosphiting agents at moderate temperatures. Our invention is based upon the unpredictable and valuable discovery that phosphoric and phosphorous acid esters of semi-drying oils, fats and liquid waxes containing the group I H H can easily be obtained by blowing the desired oil, fat or liquid wax with air or oxygen, with or without a promoter, under moderately elevated temperature conditions and then treating the blown oil thus obtained with phosphoric, phosphorous or hypophosphorous acid or with one of their various pyro" acids. While we do not confine ourselves to any particular explanation of what happens to these oils fats and liquid waxes during the blowing operation, it is our belief that the reaction between oxygen and the double bond of the ethylene group or groups present in these materials may result in a structure As it is known that ethylene oxide reacts readily with phosphoric acid, we have concluded that the production of structures (I) and (II) will explain the reactivity of blown semi-drying oils with acids of phosphorus. The literature of organic chemistry contains many theories as to the non-volatile products of reaction of air or oxygen on the semi-drying oils. However, none of these theories explains the ease of reaction between a blown semi-drying oil and an acid of phosphorus. Some have maintained that hydroxylation takes place when neats-foot oil, for example, is blown to a specific gravity of about 0.97033: As pointed out in Lewkowitsch, Chemical Technology and Analysis of Oils, Fats and Waxes, vol. 3, p. 182, 6th ed., blown oils of this type are insoluble in absolute ethanol, but soluble in petroleum fractions. In general, this is the reverse of the solubility characteristics of the 'hydroxylei ted triglyceride castor oil. The fact that the acetyl value of semi-drying oils is raised by blowing does not in any way prove that the hydroxylation of the double bond takes place, since structure (I) and probably structure (II) given above, will react with both acetic acid and acetic anhy dride. The pertinent point to consider here-is that we are not, in accordance with our invention, reacting a normally hydroxylated .oil, with an acid of phosphorus, but are reacting a blown 011, the structure of which has not been identified. Furthermore, if the acetyl value of these blown semi-drying oils is a measure of hydroxylation, it can inno way explain the degree of solubility of these phosphated oils and their salts in water.

Further evidence of the fundamentally different chemical structure and novelty of the compounds produced in accordance with our process is obtained from the following considerations: Hydroxy alkyl compounds react with 100% phosphoric acid with diiilculty to give mon-alkyl phosphates. Phosphates are prepared by reacting a compound such as castor oil with chlorides of phosphorous or anhydrides of phosphoric or phosphorous acid. If the usual theory that semi-drying oils are merely hydroxylated by blowing, the blown oil would have to be phosphated as indicated and would not be phosphated in the manner referred to in the preceding paragraphs. As. the blown semi-drying oils are, in accordance with our invention, readily phosphated with 75% phosphoric acid, this clearly shows that the hydroxylation theory is in error and that the presence of an intermediate product is required to explain the phosphation of these blown oils. Even if the hydroxylation theory could be conceded to be correct, our phosphated oils differ fundamentally from those of the prior art, since they result, not only from esterification (phosphation or phosphition) of hydroxyl groups normally present in the oil or added thereto by oxidation, but also because of the addition of the phosphate or phosphito group to the carbon chain at the position originally occupied (before blowing) by an unsaturated linkage.

The presence of hydroxyl group has not been unequivocally proved but there is strong evidence for the belief that it is present.

In the following examples and description, we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof.

In general, we prefer to employ for purposes of our invention oils having an iodine value between 55 and 140, preferably oils having an iodine value between 60 and 90. While it is impractical to list in detail all of the various semi-drying oils which are susceptible of blowing and phosphation or phosphition in accordance with our invention, typical examples of such oils include vegetable oils such as olive, castor, teaseed, corn, peanut, linseed, cottonseed, soyabean, rapeseed, and kapoc seed oils; marine animal oils suchas sperm, men- Oils of the above general types are blown, in accordance with our invention; by passing air or oxygen into a body of the oil, preferably under moderately elevated temperature conditions, with or without the use of pressure. Good results have been obtained by employing temperatures between 1'5 and 200 C. although in general temperatures from 150-190 C. have been found preferable.

Any suitable oxidation catalyst'may be employed such as fatty acid salts or oxides of copper, nickel, cobalt, chromium, aluminum, iron, zinc, magnesium, mercury, molybdenum, silver and vanadium.

When av semi-drying oil is blown the following chemical and physical changes take place: The iodine value falls, while the viscosity, specific gravity, refractive index, saponification equivalent and acetyl value rise. The chemical reactivity of the material increases from zero to an appreciable amount with acids of phosphorus. One can, by following the changes in one or more of the above physical characteristics, determine at what point to stop blowing any particular oil to obtain an oil that will react with an acid of phosphorus to give the desired solubility characteristics. For

example, if neats-foot oil is blown to a specific gravity of 7 and subsequently phosphated, it will have solubility and viscosity properties different from those of the phosphated oil obtained, for example, by reacting an olive oil blown to a specific gravity of While no hard and fast rules can be laid down which will cover every case, it may be said that, in general, the blowing of the semi-drying oil in question should be carried to the point where an 40 increase in specific gravity measured at 20 C. is

haden and whale oils, animal oils such as neatswithin the range of 0.015 to 0.10 unit.

Once the phosphated oil is obtained by the procedure described above and to be more specifically set forth in the following examples, it is converted to the desired water-soluble salt form by treatment with any suitable base such as sodium, potassium, magnesium, calcium or ammonium hydroxides, an amine such as cthylamine, triethylamine, diethylcyclohexylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, naphthenylamine, cetylamine, monofurfurylamine, difurfurylamine, trifurfurylamine, monotetrahydrofurfurylamine, ditetrahydrofurfurylamine, monotetrahydrofurfurylamine, ditetrahydrofurfurylamine, tritetrahydrofurfurylamine, cyclohexylamine or other suitable base. Conversion to the salt form is essential in order to convert these valuable new compounds into water-soluble compounds, the phosphated or phosphited oils themselves being relatively only slightly soluble in water.

In general, the solubility of these oils in solvents such as ethanol, butanol, carbitol and the like is excellent. The solubilities of the oils vary considerably with the salt prepared therefrom. For example, the triethanolamine salt of phosphated blown neats-foot oil is insoluble in ligroin, while the naphthenylamine salt is readily soluble in this solvent.

As indicated'above, any of the -ous or -ic acids of phosphorus may be employed for phosphating or phosphiting blown oils in accordance with our invention. Typical examples of such acids are phosphoric acid, metaphosphoric acid, monosodium phosphate, pyrophosphoric acid, tetraphosoils in accordance with our invention will be more' readily understood by reference to the following examples.

Example 1 Five gallons of a commercial grade of neatsfoot oil is placed in a 50-1 glass flask and heated with stirring to 150-160 C. and air is passed in with vigorous stirring. Usually there is a socalled induction period during which no appreciable physical or chemical changes take place in the properties of the oil; from this point on the viscosity of the oil rapidly changes. When the desired viscosity is reached (in this case 0. 96533) blowing is stopped. Obviously, the time needed for blowing varies with the rate of addition of air, stirring, amount of naturally occurring antioxidant in the oil, and the like.

When oxygen instead of air is employed, the process is carried out in exactly the same way, but the time of blowing is shortened. Similarly, if oxidation catalysts are employed, the time is still further shortened.

The above procedure, or an appropriate modi- "fication thereof (to adapt the procedure for the treatment of any given oil) may be employed in the blowing and phosphation or phosphition of a variety of difierent oils. Typical examples of the procedure are given below:

Example 2 100 g. of a "blown castor oil with a specific gravity of 1.0115" are heated at 100 C. with 24 g. of sirupy phosphoric acid for 3 hr. and the prodnot is washed several times with water. The reaction product is a thick, dark colored, fluorescent oil which is soluble in water when neutralized with a base such as sodium or potassium hydroxide, ammonium hydroxide, ethylamine, triethanolamine, choline, brucine, cyclohexylamine, etc.

Example 3 100 g. of a blown neats-foot oil with a specific gravity of are heated with 70 g. of 75% phosphoric acid at 60 C. for 8 hr. and. the product is washed with water several times and dried. The orange-colored, viscous oil produced is soluble in water when neutralized with a base.

Good result can be obtained with specific gravities as high as 0. 99 f3: Example 4 50 g. of a blown" olive oil with a specific gravity of 0. 954: are treated in the cold with 10 g. of phosphorous pentoxide and 2 cc. of water. The reaction product is well washed with water and dried. The clear thick oil obtained is soluble in a basic solution.

Example 5 g. of a "blown sperm oil with a specific gravity of are heated at for 4 hr. with 10 g. of sirupy phosphoric acid and 0.1 g. of concentrated sulfuric acid. The heavy oily product is washed with water, dried under reduced pressure, and neutralized.

Example 6 500 g. of a. "blown" rapeseed oil with a specific gravity of 0.966 is warmed on the steam bath with 400 g. of pyrophosphoric acid for 10 hours.

The reaction product is worked up as previously described. Salts may be prepared from any desired organic or inorganic bases.

Example 7 g. of neats-foot oil is "blown in the presence of 20 g. of 85% phosphoric acid at 125 in a copper reaction vessel. The reaction product resembles that of Example 3.

1 Example 8 100 g. of blown kapoc seed oil (sp. gr. 0. 95023:; I. V. 85)

is reacted as previously described with 25% crystalline phosphoric acid. The reaction product is worked up and salts are prepared as indicated above.

Example 9 100 g. of a blown acetylated castor oil prepared by actylating castor oil and blowing at Example 10 100 g. of blown castor oil is heated with 25 g. of phosphorous acid at 115 for 5 hours with stirring. The product is then neutralized with triethanolamine and is soluble in warm water.

In place of blown castor oil, we may use neatsfoot, sperm, olive, teaseed, soyabean, rapeseed, corn, men-haden, carnauba, japan wax, etc.

Example 11 Example 12 100 g. of blown sperm oil are heated with a mixture of 40 g. of phosphorous acid and'30 g. of phosphoric acid at 90-120 for 4 hours. The trimethylbenzyl ammonium hydroxide salt is water-soluble.

Example 13 1.00 g. of blown carnauba wax are reacted with 60 g. of phosphorous acid as above. The product is an oil having physical properties similar to the products of Examples 1-12.

Example 14 A mixture of 50 g. of blown soyabean oil and 50 g. of blown teaseed oil is reacted with 70 g. of phosphorous acid as above and neutralized with a mixture of potassium hydroxide and dibutylamine to obtain a water-soluble oil.

Example 15 A mixture oi 50 g. 01' blown soyabean oil and 50 g. of blown teaseed oil is reacted with '10 g. of phosphorous acid as above and neutralized with a mixture oi potassium hydroxide and dibutylamine to obtain a product similar to that of Example 14. I

It is noteworthy that in each of the above examples yields of 95% or higher of phosphated or phosphated oil are attained.

As indicated above, we have attained an unpredictable and hitherto unknown result in that we have provided a method for phosphating naturally-occurring oils, fats and liquid waxes not containing free hydroxyl groups or of phosphating or phosphiting oils containing uch groups by a wholly different mechanism resulting in the production or new compounds possessing solubility properties not possessed by related phosphated or phosphated oils of the prior art. In accordance with prior art methods it is not possible to phosphate an oil not containing a tree hydroxyl group. This is a result, however, which is easily obtainable by the procedure herein described because of the fact that the double bond or bonds of the semi-drying oil is attacked by oxygen to form either of the two structures (I) and (H) and the subsequent phosphation or phosphition of this structure. Even in the case of a naturally-occurring hydroxylated oil containing unsaturated linkages,

the evidence points very definitely to the fact of this effect of oxygen on the unsaturated linkage to produce a structure such as (I) and (II) which is subsequently phosphated or phosphited by the appropriate agent. I

It will be obvious from the above description of our invention that we have in fact produced an entirely new class or chemical compounds, that is, phosphated oils in which the phosphate or phosphito group is attached to carbon by breaking a carbon-to-oxygen linkage rather than by esterification oi a pre-existing free hydroxyl group. These new chemical compounds, possessing opposite solubility characteristics from the phosphated or phosphited oils derived from the phosphation or phosphitlon oi hydroxylated oils, possess many advantages over known materials and-possess outstanding merit as surface-active agents, dispersing agents, textile lubricating and anti-static agents, and for many other purposes.

What we claim is:

l. The process of producing a modified oil which comprises blowing an unsaturated organic compound selected from the group consisting of the semi-drying oils, fats and waxes at a moderately elevated temperature and thereafter treating the blown compound with an acid of phosphorus, whereby a phosphato or phosphito group is attached to carbon through a carbonoxygen-phosphorus linkage.

2. A composition of matter resulting from blowing an unsaturated organic compound selected from the group consisting of the semidrying oils, fats and waxes at a moderately.

elevated temperature and thereafter treating the blown compound with an acid of phosphorus, said composition being characterized by the fact that a phosphato or phosphlto group is attached to carbon through a carbon-oxygen-phosphorus linkage.

3. The product of claim 1 in which the composition is phosphated blown olive oil.

4. The product of claim 1 in which the composition is phosphated blown neat's-ioot oil.

5. The product of claim 1 in which the com- 

